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DOI: 10.1055/s-2006-951542
A Novel Cyclisation Strategy for the Synthesis of Lactonamycin: A New Route to Highly Functionalised Heterocyclic Rings
Publikationsverlauf
Publikationsdatum:
23. November 2006 (online)
Abstract
A novel thermal cascade reaction equivalent to the well-known [2+2+2] cycloaddition has been developed which is clean and reliable and does not involve the use of metal ions. This highly efficient method has been used to construct a model for the synthesis of the antibiotic lactonamycin. The utility of this new sequence for the formation of furans is also reported.
Key words
lactonamycin - furan - cascade - cyclisation - thermal
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References and Notes
A typical experimental procedure for the thermal cyclisation is shown below.
Synthesis of 6-Methyl-9-trimethylsilanyl-5,6,9,10-tetrahydrofuro[10,11-
e
]isoindol-7-one(15).
To 9-trimethylsilanyl-propynoic acid [4-(bromoallyl-oxy)but-2-ynyl]methyl amide (14, 0.342 g, 1.0 mmol) in toluene (10 mL) was added 1-epoxyhexene (1.00 g, 1.21 mL, 10.0 mmol). The solution was stirred at reflux for 1 h, after which time TLC showed the reaction to be complete. Toluene and 1-epoxyhexene were removed in vacuo and the product purified by column chromatography (Et2O-hexane 7:3) to give the title compound as a bright yellow oil (0.235 g, 0.9 mmol, 90% yield). 1H NMR (CDCl3): δ = 7.31 (s, 1 H, C2), 7.14 (s, 1 H, C12), 4.15-4.24 (d, 1 H, J = 18.3 Hz, C5), 3.92-4.01 (m, 1 H, C5), 3.05 (s, 3 H, C13), 2.74-2.91 (m, 2 H, C9, C10), 2.32 (d, 1 H, J = 7.0 Hz, C10), -0.11 (s, 9 H, C14, C15, C16). 13C NMR (CDCl3): δ = 173.6 (C7), 139.8 (C2), 138.3 (C4), 138.0 (C12), 137.1 (C8), 123.3 (C3), 121.4 (C11), 54.4 (C5), 32.0 (C13), 24.6 (C9), 21.9 (C10), 0.0 (C14, C15, C16). IR (neat): 3104, 2953, 2235, 1673, 1562, 851 cm-1. MS (ES+): m/z = 284 [M + Na].